Lubricant compositions



United States Patent Ufiice 3,449,249 Patented June 10, 1969 3,449,249 LUBRICANT COMPOSITIONS William S. Anderson, Oakland, Calif., assignor to Shell Oil Company, New York, N.Y., a corporation of Delaware No Drawing. Filed May 8, 1964, Ser. No. 366,189

Int. Cl. C10m 1/18, 1/32 US. Cl. 252-51.5 6 Claims This invention relates to lubricants containing the 1,3-polymer of 3-methylbutene-1.

For many years, lubricating oils have been prepared from petroleum distillate fractions by various refining techniques. To meet qualifications required by certain applications, additives have been incorporated to improve oxidation stability, viscosity index, pour point, and many other properties.

In recent years, the more stringent requirements imposed on lubricating oils have prompted research related to entirely new kinds of oils. New, more stable molecules which can provide satisfactory lubrication over wide temperature ranges, for example 65 F. to as high as 500 F., are required. Automobile manufacturers are consistently recommending longer intervals between services for new cars. Since conventional mineral oils are not always satisfactory for these applications, various synthetic oils have been investigated.

Possibly one of the earliest areas of investigation of synthetic lubricants or synthesized hydrocarbon additives is that of polyolefins. Polyisobutylene, for example, has been used as a synthetic oil for over 30 years. Even after hydrogenation, polyolefins generally were unsatisfactory lubricants because of one or more limiting deficiencies, often attributable to the structure of the polymer itself. For example, polyisobutylene, before or after hydrogenation, has relatively poor viscosity-temperature characteristics and is susceptible to degradation by heat. These undesirable characteristics are believed to be caused, at least in part, by the rigid, strained nature of the polyisobutylene molecule, a result of the repulsion or crowding of the gem-dimethyl groups on alternate carbon atoms in the main chain.

iii/ii Polyisobutyleue Polypropylene Polyethylene Polypropylene, While not having the rigid nature of the polyisobutylene molecule, has tertiary hydrogen atoms at each second carbon of the main chain (see skeletal diagram). These tertiary hydrogens are potential sites for severe oxidative attack. Ethylene polymers have very high pour points attributable to the lack of side chains. Polymers of higher alpha-olefins are deficient for various reasons; in general, they have quite low viscosities or break down very rapidly in shear gradients.

It has now been discovered that the 1,3 polymer of 3- methylbutene-l is an excellent lubricating oil constituent. This polymer, which can be realized only under certain special conditions of polymerization, provides lubricating oil constituents which possess excellent thermal, shear, and oxidation stability; The polymer may be used as a base stock, a viscosity index improver, or a building block for a larger molecule, such as a detergent.

The 1,3 polymer of 3-methylbutene-1 is Obtained by polymerizing in such a manner that the 1, 2 and 3 carbon atoms all become part of the chain, rather than only the 1 and 2 carbon atoms as is the case in the 1,2 polymer.

g Y hydried X shift fil 3-methylbutene-l l hydride shift;

- repeated ot/ A 1,3 polymer of 3-methylbutene-l Hydride shift polymers of 3-methylbutene-1 have been reported by Kennedy and Thomas, Makromolekulare Chemie, vol. 53, p. 28 '(1962) and vol. 64, p. 1 (1963). These polymers were crystalline materials of high molecular weights (about 50,000) obtained over very active Friedel-Crafts catalysts (e.g., AlCl at temperatures of -l30 C. and below. The crystallinity and high molecular weights of these polymers, of course, preclude their use as lubricants and limit their use in oil additives. Although in theory polymers of lower molecular weight could be made by operating at higher temperatures, strongly acidic catalysts such as A101 become isomerization catalysts at temperatures of 0 C. and above; furthermore, it is indicated in the articles by Kennedy and Thomas that 1,2 polymerization rather than 1,3 polymerization was obtained at higher temperatures.

The superior properties of the 1,3 or hydride-shift? polymer of 3-methylbutene-1 as compared with polyisobutylene probably derive from the insertion of another methylene group between the quaternary carbon atoms. This extra methylene group provides further separation of the gem-dimethyl groups, thus relieving molecular crowding or strain and providing a more flexible molecule. Therefore, the instant polymer has excellent shear resistance as well as a low pour point, good oxidation stability, etc. Accordingly, it is essential that a high proportion but not all of the polymer have a 1,3 structure rather than the 1,2 structure obtained in conventional polymerizations. The 1,2 polymer can be described as an ethylene chain with isopropyl groups attached to every other carbon atom in the chain. The skeletal diagram of the 1,2 polymer of 3-methylbutene-1 is compared with that of the 1,3 polymer below stable because of the presence of tertiary hydrogens on both the main chain and the side group. Therefore, a

preponderance (i.e., at least 50%) of 1,3 linkages is es-'- sential to the polymers of the inventon. The repeating unit of the 1,3 polymer is It. istpreferred that from about 60 to 98%, and more desirably 80 to 95% of the polymerizing molecules of 3- methylbutene-l have their 1, 2, and 3 carbon atoms become part of the chain; i.e., from 60 to 98% and preferably 80 to 95% of the polymerization is hydride-shift polymerization. The remainder is made up of 1,2 linkages, and groups derived from the catalyst or solvent, cyclized units, and unsaturated end groups formed by hydride removal.

There are three general areas of applicability of the present polymers in lubricating oils. They may be used (1) as oil base stocks (after hydrogenation), (2) as viscosity-index improvers (generally also after hydrogenation), and (3) as building blocks for larger molecules which require a stable, long hydrocarbon chain, such as dispersants. When used as base stocks, the hydride-shift polymers are generally preferred to be in the molecular weight range of from about 200 to about 4000, preferably 300 to 2000. These base oils generally comprise at least 50% by weight and usually 80% or more of the oil composition; however, these polymers are soluble in mineral oils and can be mixed therewith in any concentration. It is preferred to use at least 30% by weight of the 1,3 polymer of 3-methylbutene-l, more preferably at least 60%. When used as a base stock, any of the well known additives may be added to provide improved viscosity index, pour point, oxidation stability, etc.

' When used as viscosity-index improvers in mineral oils,

hydride-shift polymers of 3-methylbutene-1 are generally preferred to be in the molecular weight range of from about 10,000 to 500,000, preferably 10,000 to 200,000. These long-chain polymers can be used to increase the VI of any mineral oil or other polymer-based oil. Although the theory of VI improvement is not completely understood, it is believed to relate to a change in the physical state of solution or dispersion of the polymer molecules with a change in temperature. Desirable concentrations of the instant polymer when used as a VI improver are from about 1 to about preferably 2 to 8% by weight of the lubricating oil.

As an example of the use of the instant polymer as a VI improver, a solution of 1.5% wt. of poly-3-methylbutene-l, 10,000 molecular weight, and about 80% 1,3 linkage in a mixture of neutral mineral oils had the following viscosities:

Viscosity of Viscosity of base oil,

Dispersant additives, commonly known as detergents, are widely used in concentrations of from about 0.2 to 10% by weight to impart properties to oils which enable oxidation products, soots, resins, and other insoluble matter to remain in suspension or dispersion so that they will not alhere to metal surfaces to build up as sludge or varnish deposits. Dispersants may be made from the instant polymer by attaching polar groups, preferably nitrogen-containing polar groups, at the unsaturated end. Preferred polar groups contain only carbon, hydrogen, nitrogen, and a chalcogen, preferably oxygen. Molecular weights of the polar group are from about 100 to about 3000. Although it is preferred to have only one polymer chain attached to each polar group, it is also possible to have two or more chains attached to the group. Preferred polar groups contain at least 1, preferably 1 to 3 heterocyclic groups having from 5 to members in each heterocyclic group; for example derivatives of pyridine, pyrazine, pyrrolidone, pyrrolidine, succinimide, oxazine, quinoline, morpholine, thiophene, etc. Members of the heterocyclic group are preferably selected from the group consisting of carbon, nitrogen, oxygen, and sulfur. Examples of suitable polar groups are the maleic anhydride-polyethylene imine adducts 0 and \TA Jae-ll i NCHaCHuNHCHiCHzhII where x=l to 10. Molecular weights of the p0ly(3- methylbutene-l) suitable for this purpose are generally preferred to be in the range 200 to 10,000, preferably 500 to 3000. The adduct is formed by first reacting the poly-3-methylbutene-1 with maleic anhydride, then with a polyethylene imine of the desired molecular weight, preferably tetraethylene pentamine. Molecular weights of the dispersant generally range from about 200 to about 12,000, preferably 400 to 8000. Variants on the structure above include (1) adduct in which the @C double bond is hydrogenated, (2) adduct in which an alkenyl succinimide unit occurs at both ends of the polyimine chain, (3) adduct in which the imide structure is cyclized to imidazoline, (4) adduct in which the carbonyl groups are reduced to CH (5) adduct which is formed by reacting poly-3-methylbutene-l with HCl or HBr to obtain a longchain alkyl halide, then using that alkyl halide to alkylate polyethylene imine, (6) adduct formed by reacting the formamide with the terminally unsaturated poly-3-methylbutene-1 in the presence of ultraviolet light.

To illustrate the superior properties of the polymer of the invention, oxidation and thermal stability comparisons were made with polyisobutylene.

Example I Weight loss 2. 5% 5. 0% 10% 15% 20% Polyisobutylene C.) 280 292 308 319 326 3-methylbutene-1 C.) 315 345 401 407 415 The data indicate that higher temperatures are necessary to decompose given amounts of poly(3-methylbutene-l) than polyisobutylene; thus, the 1,3 polymer of 3-methyl butene-l is a more thermally stable material. Indeed, these results are conservative in that the lower mole weight polymer would be expected to show somewhat higher weight losses than the higher mole weight material.

Example II Oxidation stabilities of a linear polyethylene, a polyisobutylene and poly(3-methylbutene-1) were determined by oxygen absorption tests conducted at 165 C. on 10% w. solutions of polymer in a solvent of bis(p-phenoxyphenyl) ether having about two tert-butyl substituents per molecule containing 0.20% w. copper naphthenate catalyst. The 3-methylbutene-1 polymer was approximately 1,3 polymer, and had a molecular weight of about 10,000. The molecular weights of the polyethylene and some of the catalyst-leaves the reactor, it may be seppolyisobutylene were about 20,000 and 100,000, respecarated and recycled or'discarded, or may be allowed to tively. 7 pass out with the product. If the catalyst is used in the Polymer oxidation was measured by the liters of oxygen molten form, it may be separated from the reactor efiluuptake per 500 grams of solution after 100 hours of 5 ent (in which it is substantially insoluble) and recycled bubbling oxygen through the samples. or discarded. Generally, any substance in which the re- Liters O2(NTP) /500 grams actants are soluble and which does not take part in the reaction is a suitable solvent; as examples, mention may 2 absorbed 100 be made of paraflins, such as isooctane; halogenated polgethyleney 10 alkanes, such as methyl and ethyl chlorides, and methyl 5 and ethyl bromides; 1,2+dichloroethane, carbon disulfide,

' nitrobenzene, nitromethane, vinyl chloride, etc. It is pre- The lower oxygen uptake by the poly(3-methylbuteneferred to carry outthe reaction in the presence of a solindicates the superior oxidation resistance Of this polymer. vent, because dilution of the monomer shows the addi- The 3-methylbulehe-l P y 0f the invention can be tion rate of the monomer relative to the hydride shift p p n several y w ver, i is n i l h p reaction, insuring a high percentage of hydride-shift polylymelilalion takes Place in Such a manner that the P mer. Furthermore, it is generally easier to handle the uct predominates in 1,3 polymer. Verynhigh-molecularpolymer in solution. When a solvent is used, volumetric weight (e.g., solid and semi-solid) v1,3-polymers can be solvent/monomer ratios .are from about 0.5 to about 20, produced at low temperatures with, Friedel-Crafts cata- 2 preferably from about 1 to aboutlO. lysts. These high-molecular-weight materials can then be Polymerization temperatures with M(AlX catalysts cracked by well known methods to yield polymers suitare usually in the range of from about 50 C. to about able for use in lubricating oils. For example, the polymer 120 0., preferably from about 0 to about 100 C., de- Of molecular Weight 50,000 y be heated under high pending on the concentration of the monomer and the Vacuum at 425 for fifteen minutes to 8 Polymer desired molecular weight of the polymer. The polymeriza- Polyisobutylene of about molecular. Weight Preparation of 'E tion is carried out in the liquid phase. Process pressures molecular'welght mammals 18 descnbed detail are not critical, except to keep the system substantially in Kennedy a Thomas noted above! the liquid phase; autogenous pressures are generally satis- Predominantly hydride shift polymers of 3 methylfactory butene-l can also be prepared by polymerization over tetrahaloaluminate catalysts having the formul 7 Polymers prepared wlth M(A1X4)n catalysts are preferred for use in lubricating oils because these catalysts 4)n produce the desired polymer directly; cracking of high- Wherein M is a metal or a mixture f metals, especially molecular-weight polymers is sometimes accompanied by a metal f o Group I I or V of the periodic Table, other side reactions, such as rearrangement, which proespecially Li, Na, and Co; n is a whole number equal to duce undesired Properties in tha P the valence of M (i.e., n is one if M is monovalent, two if The following table illustrates the results of 3-methyl- M is divalent, etc.) and X is a halogen, preferably chlobutene-l polymerization over various tetrahaloaluminate rine, bromine or iodine. Tetrahaloaluminates are white catalysts. Product structure was determined by nuclear to greyish, brittle, low-melting crystalline solids. Some magnetic resonance and confirmed by infrared analyses examples of these compounds are NaAlCl LiAlCl to be at least about 80% 1,3 polymer in each case.

POLYMERIZAIION OF 3-METHYLBUTENE-l WITH HYDRIDE SHIFT OVER TEIRAHALOALUMINATE SALTS Experiment number 1 2 3 4 5 6 7 3rnethylbutene-1 (I),m1noles 713 799 442 539 538 Solvent (II) None IkgoHu u-OCtHn lllgooctane 4 1,2C7H4Cl3- IIII'iJiKiiZIIIII LiAZiiiIIII LiAioii'fIII Nam (31111.-. NaKiiZILLI cooii'dl'iiihI 000.101,.

28.1 4.2 .2 4.7 5.6 3.5 III, I--. III II I III 20-40 ma 04 15 ca 25 e, 0.2--- 2.0- Recovery of charge, percent w 103 1l3 11 99.6 Yield of finished polymer, percent w. ca 100 5.3 11.9 8.5 17.6 l7.5.

of feed, no-loss basis. Polymer )molecular weight (ebullio- 1,l00;i;50 890=|=40 690:1:30 (600-800) (400500) (BOO-1,000).

SOODIC 1 Experiments 1-3 were made in a stirred glass reactor with internal 5 Catalyst added as suspension in all or part of total solvent, 5 mg. cooling coil; experiments 4-7 were made in a 250 ml. stainless steel auto catalyst/ml. of solvent. clave. In the latter series, B-methylbutene-l was fed slowly and con- 4 Monomer added uniformly during entirerun period. tiuuously by means of a high pressure syringe pump. 5 Estimated visually by comparison with samples of known molecular 1 Desgibed in Daniels et al., Experimental Physical Chemistry, 1949, weight. pp. 75-

Co(AlCl AgAlCl NaAlBr Be(AlBr Mg(A1Cl )z, Lubricating compositions of the invention may also Fe(AlCl NiAlBr L1AlI etc. Hydride-shift polymcontain any well known additives such as oxidation inerization of 3-methylbutene-1 with these catalysts is dehibitors, VI improvers, extreme pressure agents, pour scribed in copending application Ser. No. 314,910, filed point depressants, antiwear agents, foam inhibitors, cor- Oct. 9, 1963, now abandoned. T051011 lphlbltors Tetrahaloaluminate catalysts can be employed in any I clalm y lIlVeIltlOhj fashion known to those skilled in the art; for example, Alulqneant eel'npesltwn q p s g ie amount the catalyst can be powdered and used as a solid (at temof a lubncatmg 011 and a Vlscoslty lPdex mcreasmg peratures below the melting point of the salt), or can be amount of a POIYG'methYIbHteDeI) havmg a molecular weight of from about 200 to about 200,000 in which a l l catal st or su orted on an inert used as a mo ten w t y pp major proportion of the polymer consists of carrier, such as porcelain, alumina, or charcoal. Monomer can be fed with or without a solvent to a reactor cm which contains the catalyst. If the catalyst is in the solid units form, the catalyst may be retained in the reactor or part 7 AH may be allowed to pass out with the reactor efiiuent. If

7 2. The composition of claim 1 in which 60 of the polymer consists of 3. The composition of claim 1 in which 80 to 95% of the polymer consists of I 0 Ha CHr-CHr- 5. A lubricant composition comprising a major proportion of a mineral lubricating oil and from about 0.2 to about 10% by weight of a dispersant consistingessentially of the addition product of (1) poly(3-methylbutene-1) in which a major proportion of the polymer consists of units 8 having a molecular weight of from 500 to 3000, (2) maleic anhydride, and

(3) tetraethylene pentamine.

6. A hydrocarbon lubricating oil which contains an oil soluble viscosity index modifier in amount sufficient to improve the viscosity index of the lubricating oil said modifier consisting of 1,3-poly-3-methyl-1-butene produced by polymerizing 3-methyl-1-butene at a temperature below 0? C. in the presence of an aluminum halide cata- 1yst.. 4

. v 4 References Cited UNITED STATES PATENTS 2,637,720 5/1953 Schneider et a1 252-59 X 2,779,753 1/1957 Garabrant et a1. 252-59 X 2,825,721 3/1958 Hogan et al 252-59 X 3,024,195 3/1962 Drurnmond et a1. 252-515 3,076,764 2/ 1963 'Hansen'et a1 252-59 3,131,150 4/1964 Stuart et a1 252-515 X 3,154,560 10/1964 Osuch 252-515 X 3,182,024 5/1965 Stuart et al 252-50 3,219,666 1 1/1965 Norman et a1 252-515 X FOREIGN PATENTS v 605,571 9/1960 Canada.

DANIEL E.WYMAN, Primary Examiner.

W. CANNON, Assistant Examiner.

US. Cl. X.R. 252-475, 59 

5. A LUBRICANT COMPOSITION COMPRISING A MAJOR PROPORTION OF A MINERAL LUBRICATING OIL AND FROM ABOUT 0.2 TO ABOUT 10% BY WEIGHT OF A DISPERSANT CONSISTING ESSENTIALLY OF THE ADDITION PRODUCT OF (1) POLY(3-METHYLBUTENE-1) IN WHICH A MAOR PROPORTION OF THE POLYMER CONSISTS OF 